Dr. M.A. Kazi Institute of Chemistry, University of Sindh, Jamshoro, Sindh, Pakistan
2
Institute of Physics, University of Sindh, Jamshoro, Jamshoro, Sindh, Pakistan
3
Institute of Advanced Research Studies in Chemical Sciences,University of Sindh, Jamshoro, Sindh, Pakistan
Abstract: - The study under investigation discovers the sorption conduct of resin used as an adsorbent toward
metal ions and specified the percent sorption for the metal that reduced with rise in pH, above pH 6.The degree
of uptake for resin initially was fast (88-90 %), creating equilibrium within sixty minutes for Copper. The resin
exhibit the extreme percent sorption (86 - 88 %) for Nickel ranging contact time between sixty minutes; further
than the described range the surge in % sorption was not recognized. The flow rate, isotherms and
thermodynamic parameters were also examined for both the metal ions. PMBMNen effectively eradicated
heavy amounts of metals from the real water samples.
Keywords: - Adsorbent, column method, isotherms, Metal ion uptake, resin.

I.

INTRODUCTION

Number of reactions including heterogeneous polymerization in which motorized stirring is used for
amalgamating monomer to synthesize polymers, and is used to form polymer adsorbents Formation of
hyperactive cross-linked adsorbents is an example [1,2]. As the process of adsorption proceeds in a solution the
adsorbate molecule is haggard from that greater part of solution towards the adsorbent segment, remaining
dominating forces like adsorbent, solute, are the reasons held responsible for the uptake [3-5]. Catalytic
flourimetric process is a widely described method regarding Cu (II) metal [6, 7]. Researchers worldwide have
tremendous contributions on chemical transformations regarding resins (polymeric) resulting enhancement in
adsorption dimensions on adding different functional groups [8-11].
The study under investigation examines the uptake behavior of the two metals on resin PMBMNen,
used as an adsorbent. Under improved conditions quantitative sorption was accomplished for the copper and
nickel metal ions on prepared compound, PMBMNen. The inspected metals were desorbed magnificently with
five milliliters of Hydrochloric acid (0.1M).
11. Experimental Work
The newly synthesized resin PMBMNen was recrystallized from rectified spirit to eliminate impurities
and which also improved its melting point, by showing rise in melting point. The C.H.N analysis of compounds
was lead at Carlo Elba Devon U.K and exposed findings that were very near to the calculated values. The
uptake studies were reinforced by batch and column methods.
2.1 Batch Method
Hundred mg of hundred mesh size of polymer PMBMNen was poured in a flask that was conical
comprising aqueous solutions (ten microgram per milliliters) of the metals. The pH of the solutions was
accustomed to the desired value via adaptation of appropriate buffers. Suspension of PMBMNen on known
concentration of metals (ten milliliters) were shaked with hundred rotations per minute on a thermostatic
shaker.
Filtrations and several washings with deionized water were accomplished. The filtered product and washings
were examined via atomic absorption spectrophotometer. The found results were used to compute the % of
sorption by the compound and the (Kd) values were also evaluated.
2.2. Column Method
Five hundred milligrams of PMBMNen be located in a glass column six mm one hundred and fifty mm). The
compound was adapted with twelve milliliters of Buffer possessing pH six.

3.1 Metal ion uptake by Batch method
3.1.1) Effect of pH:
Effect of pH is a chief step in attaining the adsorption quantitatively regarding polymeric compounds.
The effect of pH was speckled ranging (one to nine) for metals copper and Nickel. The more basicity of
Nitrogen of C=N, group at pH directly above the said results is the cause for removing high % of metals at this
raised pH, whereas at low pH protonation of azomethine group resulted. At pH six resins was capable to
remove eighty eight % of Copper ions and eighty four % of Nickel metal ions. Above the said pH a fall in %
sorption was perceived as shown in “Fig. 1”.
3.1.2 Effect of contact time/ equilibrium time
Equilibrium time was examined within the range ten to hundred minutes. Hundred mg of PMBMNen
was used with hundred RPM speed of shaking, by taking twenty milliliters of ten microgram/ milliliters of both
the metals. Percent adsorption of copper (II) ions was found elevated as compared to the other metal, and could
be due to less action of the synthesized compound towards Nickel (II) ion .The proportion of uptake of
PMBMNen in the preliminary stage was firm forming equilibrium in one hour “Fig 2”.
3.1.3 Effect of Volume
The optimum volume obtained was twenty one and twenty milliliters for supreme % sorption of Cu (II) and Ni
(II) ions, for PMBMNen “Fig. 3”.
3.1.4 Effect of Metal ion Concentration
The sorption conduct of concentration of metal ion for the resin was calculated ranging ten to hundred µg/ml.
On aggregating the concentration quantity of uptake improved and could be due to the available sites present in
resin, as at greater concentrations possibility of more available sites are not obtainable for adsorption.
3.2 Metal Ion Uptake Studies by Column method.
3.2.1 Effect of Flow rate
The flow rate designated for the maximum sorption ranged within one to eight milliliters/min at the adjusted pH
it was quite evident from the studies that on increasing the flow rate greater than 1 ml min -1for the metals, the %
adsorption decreased “Fig. 4”.
3.2.2 Desorption
The desorption of the Cu(II) and Ni(II) metals were resulted by shaking of five hundred mg resin with
the solutions of metals, on ideal conditions. The compound was filtered & washed with sum of concentrations
ranged within (0.1) and (1 -10 ml) volumes of mineral acid, maximum recovery of 90 -92 % of both the metals
with 0.1M Hydrochloric acid within five milliliters of volume was attained.
3.3 Adsorption Isotherms
Langmuir”, “Freundlich” and Dubinin- R isotherms were applied on the data. Fruendlich plot between
log Cads (mol g-1) and log Ce (mol/dm3) via using “equation 1” exhibited linearity for the synthesized resin.

log Cads  log K 

1
log Ce
n

(1)

The curve helped in assessing the multilayer adsorption efficiency designated by K mmol g -1, and to estimate
the strength of uptake. The graph of Fruendlich isotherm exposed straight lines, as shown in “Fig.5” the
intensity of adsorption 1/n was also calculated from intercept and slope on lesser balanced concentrations the
adsorption capacity was repressed to approximate extent, as showed via rate of Freundlich constant 1/n is less
than 1. The Freundlich constants K, n were intended as of the intercept and slope of the plot. The Langmuir
constants were evaluated from intercept and slope of lined plot using “eqauion 2” as shown in “Fig.6”.

The straight line signifies that data fitted well to the isotherm. The separation factor RL was also considered
and was found in the range that the utmost favorable separation factor for the resin PMBMNen. The DubininRadushkevich isotherm was also examined for the newly formed resin was plotted among lnC ads and ɛ2
presented linearity using “equation 3”.

ln Cads  ln X m  ß 
E

(3)

1
 2

(4)

The energy of adsorption, E (calculated from the slope of D-R graph) as in “Fig. 7”, which is the free
energy of one mole of solute to the adsorbents surface, was 12.91 for Ni (II) and 12.50 for Cu (II) ions for
PMBMNen, Table [1]. The results ranged in twelve to thirteen kilo joules per mole, expected for ion exchange.
The Cu (II) and Ni (II) ions were effectively sorbed on PMBMNen.
3.4 Sorption Kinetics
At the raised pH the kinetics of both the metals that is copper and nickel were assessed via alteration in
sorption compared to time in (min). Morris Weber equation 5 and Lagergren equation 6 were used to calculate
the results, as shown below,

qt  Rid

(5)

t

log q e  q t

  logq e



kt
2.303

(6)

Rd the rate constant was calculable from slope of the plot, “qt” verses “t”. The graph illustrates that as the
agitation time was at maximum it diverged for the metal nickel. For PMBMNen the Rd values evaluated from
the slope of graph were 5.2 ± 0.05, ± 6.5 ± 0.07, 5.5 ± 0.04 and 6.7 ± 0.9 µmolg-1 min for both the metals “Fig.
8” & “Fig. 9”.
3.5 Sorption Thermodynamics
The results of sorption were exposed to survey the parameters regarding thermodynamics, by calculating (K c)
the equilibrium constant, all the useful data regarding temperature were examined within two hundred and
eighty three to three hundred and twenty three kelvin. At improved settings, for sorption of both the metal ions
onto the resin, PMBMNen. The plot between log Kc was designed against 1/T (T in K) using “equation 7”,
providing linear relationship.
ln K c  

Adsorption Studies of Copper (II) and Nickel (II) Ions on Polymeric Resin PMBMNen
3.6 Interference Study
The influence of cations & anions sodium, potassium, Magnesium and Chloride, Bromide and SO 4 on the
uptake conduct of PMBMNen was considered. PMBMNen was treated through fifty microgram per milliliters
for the mentioned cations. The optimal pH of solution of metals was designated for the period of twenty four
hours .The findings pointed out that the capacity of uptake of both the metals was not bothered by the above
cations and anions.
3.7 Constancy of the Sorbent
The stability of the resin was achieved and was reprocessed ten times fluctuating among one to five percent
intended for sorption, declaring the resin PMBMNen correct for “sorption”.
4. Applications toward Actual H2O Samples
For the elimination of significant metals from surface water samples, of the cultivation lands, Column
technique was applied. The samples were filtered and metals were efficaciously removed under enhanced
conditions from surface water samples, and were studied via Atomic Absorption spectrophotometer. The results
showing percent of sorption and percent recoveries are shown in Table 3.

III.

CONCLUSION

The present study focuses on newly synthesized polymeric resin PMBMNen as an adsorbent. The resin
was also used to estimate the sorption capability of metal ions from surface water from different agriculture
lands. The metals were desorbed well with five milliters of Hydrochloric acid (0.1M). The data showed that the
percent of metal adsorption was greater for Copper than the Nickel complexes. The percent sorption for the
metal reduced with rise in pH, above pH 6.The degree of uptake for resin initialy was fast (88-90 %), creating
equilibrium within sixty minutes for Copper. The resin exhibit the extreme percent sorption (86 - 88 %) for
Nickel ranging contact time between sixty minutes; further than the described range the surge in % sorption was
not recognized. The flow rate” of one milliliter per minute was enhanced for the adsorption of metal ions on
PMBMNen. The isotherms as well as the thermodynamic parameters were estimated successfully for both the
metals. The data presented that the sorption capability for the metals was not pretentious by interference of
diverse cations and anions. PMBMNen successfully eliminated 98% of Cu (II) and 95% of Ni (II) ions from
sample 1 and 97% Cu (II) and 96% of Ni (II) ions from sample 2 and 98% of Cu (II) and 97% of Ni (II) ions
from sample 3. Under heightened circumstances quantitative adsorption was accomplished for the metal ions on
resins PMBMNen. The positive results gained offered an idea that such type of compounds may be prepared
and can be used as adsorbents to remove substantial metals.